Patent GB-957022-A (GB)
Title: A process for the production of unsaturated aliphatic nitriles
IPC: B01J27/186
Filed: 1960-07-18
Abstract: Acrylonitrile and methacrylonitrile, together with the corresponding saturated nitriles, are prepared by reacting propylene or isobutylene with ammonia and molecular oxygen in the gas phase at elevated temperature in the presence of a catalyst comprising a solid phosphoric acid (see below) activated by at least one compound of one or more of the following metals: Ti, Mn, Fe, Co, Ni, Cu, Zn, Ag, Au, Cd, Sn, Ce, Pb, Bi, Th, V, Nb, Ta, U, Mo and W.  "Solid phosphoric acid" means a mixture or compound of a phosphoric acid with an adsorption material or reagent, in which the phosphoric acid may be physically or chemically bonded, or bonded in any transitional stage between these two extremes, and which exist as mechanically strong and hard masses or compositions under the reaction conditions. Such catalyst masses are acidic, changing p-dimethylaminoazobenzene from yellow to red and phenylazodiphenylamine from yellow to violet. Suitable catalysts may be prepared by mixing a phosphoric acid with the adsorbent or reagent in the presence of the activator, or by impregnating a solid phosphoric acid with the activator or activators, and heating.  Suitable adsorbents or reagents are oxides such as those of Al, Mg, Th, Ti, Zr and B, and their mixtures, silicic acid, boric acid, silicates such as diatomaceous earth, kieselguhr and silica gel; fuller's earth, florida earth, and clays such as bentonites, montmorillonites and acid-treated clays. Suitable phosphoric acids are ortho-, pyro-, tri-, tetra- and other polyphosphoric acids. In examples the catalysts used are compounded of the following components and then heated: (1) BPO4 and Cu(NO3)2; (2) boric acid, H3PO4, aluminium acetate, Cu(NO3)2 and ammonium molybdate; (3) H3PO4, molybdic acid, Bi(NO3)3 and BPO4; (4) molybdic acid, H3PO4; Bi(NO3)3, TiO2 and polyphosphoric acid; (5) BPO4, and ammonium molybdate or tungstate; (6) BPO4, ammonium molybdate and one of Fe(NO3)3, Co(NO3)2 or Ni(NO3)2; (7) Cu(NO3)2, polyphosphoric acid, TiO2 and Nb2O5; or boric acid, TiO2, Nb2O5, Cu(NO3)2 and H3PO4; (8) boric acid, H3PO4, Cu(NO3)2, phosphomolybdic acid, ZrO2 and polyphosphoric acid, (9) tungstic acid, Cu(NO3)2 and BPO4; (10) polyphosphoric acid, Cu(NO3)2, Ta2O5 and TiO2; (11) gold in aqua regia, and BPO4; (12) BPO4, SnCl2 and H3PO4; (13) boric acid, H3PO4, Bi(NO3)3 and Cu(NO3)2; (14) Ni(NO3)2, tungstic acid and BPO4; (15) BPO4, FePO4 and H3PO4; (16) BPO4, Cu(NO3)2, AgNO3 and H3PO4; (17) phosphomolybdic acid, Bi(NO3)3, silicic acid and H3PO4; (18) Cu(NO3)2, ammonium molybdate, H3PO4 and silicic acid; (19) BPO4, Pb(NO3)2, H3PO4 and ammonium molybdate; (20) AgNO3, ammonium molybdate and BPO4; (21) Ce(NO3)3, ammonium molybdate and BPO4; and (22) Cu(NO3)2, ammonium metavanadate, polyphosphoric acid and TiO2. Other specified activators are Mn(NO3)2, Zn(NO3)2, Cd(NO3)2, Th(NO3)4 and uranyl acetate.  Specification 867,438 is referred to.  Reference has been directed by the Comptroller to Specification 874,593.ALSO:Catalysts for the production of acrylonitrile and methacrylonitrile (see Division C2) comprise a solid phosphoric acid (see below) activated by at least one compound of one or more of the following metals: Ti, Mn, Fe, Co, Ni, Cu, Zn, Ag, Au, Cd, Sn, Ce, Pb, Bi, Th, V, Nb, Ta, U, Mo, and W.  "Solid phosphoric acid" means a mixture or compound of a phosphoric acid with an adsorption material or reagent, in which the phosphoric acid may be physically or chemically bonded, or bonded in any transitional stage between these two extremes, and which exist as mechanically strong and hard masses or compositions under the reaction conditions.  Such catalyst masses are acidic, changing p-dimethylaminoazobenzene from yellow to red and phenylazodiphenylamine from yellow to violet.  Suitable catalysts may be prepared by mixing a phosphoric acid with the adsorbent or reagent in the presence of the activator, or by impregnating a solid phosphoric acid with the activator or activators, and heating. Suitable adsorbents or reagents are oxides such as those of Al, Mg, Th, Ti, Zr and B, and their mixtures, silicic acid, boric acid, silicates such as diatomaceous earth, kieselguhr and silica gel; fuller's earth, florida earth, and clays such as bentonites, montmorillonites and acid-treated clays.  Suitable phosphoric acids are ortho-, pyro-, tri-, tetra- and other polyphosphoric acids.  In examples the catalysts used are compounded of the following components and then heated: (1) BPO4 and Cu(NO3)2; (2) boric acid, H3PO4, aluminium acetate, Cu(NO3)2 and ammonium molybdate; (3) H3PO4, molybdic acid, Bi(NO3)3 and BPO4; (4) molybdic acid, H3PO4, Bi(NO3)3, TiO2 and polyphosphoric acid; (5) BPO4, and ammonium molybdate or tungstate; (6) BPO4, ammonium molybdate and one of Fe(NO3)3, Co(NO3)2, or Ni(NO3)2; (7) Cu(NO3)2, polyphosphoric acid, TiO2 and Nb2O5; or boric acid, TiO2, Nb2O5, Cu(NO3)2 and H3PO4; (8) boric acid, H3PO4, Cu(NO3)2, phosphomolybdic acid, ZrO2 and polyphosphoric acid; (9) tungstic acid, Cu(NO3)2 and BPO4; (10) polyphosphoric acid, Cu(NO3)2, Ta2O5 and TiO2; (11) gold in aqua regia, and BPO4; (12) BPO4, SnCl2 and H3PO4; (13) boric acid, H3PO4, Bi(NO3)3 and Cu(NO3)2; (14) Ni(NO3)2, tungstic acid and BPO4; (15) BPO4, FePO4 and H3PO4; (16) BPO4, Cu(NO3)2, AgNO3 and H3PO4; (17) phosphomolybdic acid, Bi(NO)3)3, silicic acid H3PO4; (18) Cu(NO3)2, ammonium molybdate, H3PO4 and silicic acid; (19) BPO4, Pb(NO3)2, H3PO4 and ammonium molybdate; (20) AgNo3, ammonium molybdate and BPO4; (21) Ce(NO3)3, ammonium molybdate and BPO4; and (22) Cu(NO3)2, ammonium metavanadate, polyphosphoric acid and TiO2.  Other specified activators are Mn(NO3)2, Zn(NO3)2, Cd(NO3)2, Th(NO3)4 and uranyl acetate.  Specification 867,438 is referred to.  Reference has been directed by the Comptroller to Specification 874,593.